CN104031277A - Polyimide film and manufacturing method thereof - Google Patents
Polyimide film and manufacturing method thereof Download PDFInfo
- Publication number
- CN104031277A CN104031277A CN201410083446.5A CN201410083446A CN104031277A CN 104031277 A CN104031277 A CN 104031277A CN 201410083446 A CN201410083446 A CN 201410083446A CN 104031277 A CN104031277 A CN 104031277A
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- Prior art keywords
- film
- polyimide film
- polyamic acid
- gel
- polyimide
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Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 230000005540 biological transmission Effects 0.000 claims abstract description 26
- 229920005575 poly(amic acid) Polymers 0.000 claims description 90
- 108010025899 gelatin film Proteins 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 42
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 26
- 238000007669 thermal treatment Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000010408 film Substances 0.000 description 155
- 230000000873 masking effect Effects 0.000 description 32
- 238000002156 mixing Methods 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 19
- 239000000203 mixture Substances 0.000 description 15
- 239000003960 organic solvent Substances 0.000 description 14
- -1 aromatic tetracarboxylic acid Chemical class 0.000 description 12
- 239000004642 Polyimide Substances 0.000 description 11
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 10
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 8
- 150000004984 aromatic diamines Chemical class 0.000 description 8
- 238000005336 cracking Methods 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 8
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 210000002469 basement membrane Anatomy 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 229940059936 lithium bromide Drugs 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000892 gravimetry Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 210000004379 membrane Anatomy 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- CTLMDLQGWKKYRZ-UHFFFAOYSA-N CCCC(C)(CCC)NC Chemical compound CCCC(C)(CCC)NC CTLMDLQGWKKYRZ-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- JRDBISOHUUQXHE-UHFFFAOYSA-N pyridine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)N=C1C(O)=O JRDBISOHUUQXHE-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The present invention relates to a polyimide film and a manufacturing method thereof. According to the polyimide film and the manufacturing method thereof, problems of film fracture and flow wrinkling are prevented from happening easily. The present invention specifically relates to a polyimide film having a thickness less than 8.0 [mu]m and the manufacturing method thereof. The fracture broadcasting resistance of the polyimide film is larger than 1.7 N/mm, the minimum value of the ultrasonic transmission speed of the polyimide film is larger than 2.0 Km/s, and the thickness of the polyimide film is less than 8.0 [mu]m.
Description
Technical field
The present invention relates to polyimide film as thin as a wafer.
Background technology
Obtain polyamic acid polymer solution by making aromatic diamine and aromatic tetracarboxylic acid's dianhydride carry out polyreaction in organic solvent, then make this polyamic acid polymer fluid be formed as membranaceous, make its hot dehydration closed-loop and/or chemical dehydration closed loop, be imidization and polyimide film, due to thermotolerance, insulativity, and mechanical characteristics (with respect to the weather resistance of external force) excellence, therefore be widely used in the electrically insulating material of electric wire, thermal insulation material, the basement membrane of flexible printed board, band for belt automatic welding (tape automated bonding) the carrier band film of use of unicircuit and the lead frame attachment of unicircuit, and with the protection of electroconductive circuit, in covering (cover lay) purposes that insulation is object etc.
In these purposes, flexible printed board to be to form circuit pattern on the basement membrane soft and thin, and the structure of having implemented on its surface to cover is as basic structure, due to its outstanding function such as flexible, and is widely used in electronic technology field.But, along with the progress of field engineering in recent years, need the densification of wiring, accompany therewith, also require gradually high resistance to bend(ing).But, if flexible printed board in the past carries out multiple stratification, small-bend radius, have after life-time service the such problem of broken string occurs, can not get having the substrate of sufficient resistance to bend(ing).
One of method improving as miniaturization and the bendability of flexible printed board, the effectively filming of polyimide.But film dies down due to filming, produce film and be easy to fracture, be out of shape such problem.In addition, if film thickness is thinner, the rigidity of film is lower, and therefore the planarity of film is poor, is easy to produce fold while conveying, produces the problems such as bad that apply, and yield rate reduces.Even if therefore expect to develop as film and also there is sufficient resistance to tearing, the thin polyimide film of operability excellence when the good and conveying of planarity.
In addition, polyimide film obtains as follows: make with 4, to be the aromatic diamine of representative carry out polyreaction with the aromatic tetracarboxylic acid's dianhydride taking pyromellitic acid anhydride as representative to 4 '-diamino-diphenyl ether in organic solvent obtains polyamic acid polymer solution, then make this polyamic acid polymer fluid be formed as membranaceous, make its hot dehydration closed-loop and/or chemical dehydration closed loop, i.e. imidization.Particularly, be added with the solution of the tertiary amine of more than stoichiometry dewatering agent and catalytic amount by polyamic acid polymer solution or in this solution, curtain coating or coating on drum or endless belt and become membranaceous, dry approximately 5～10 minutes of temperature by this film below 100 DEG C, acquisition has the film of the polyamic acid polymer of self-supporting.Then, peel off and use multiple pins, fixture that film end is fixed from support it, be directed in tentering formula baking oven, stretch while be heated to gradually approximately 100～300 DEG C, making solvent seasoning, obtain base film (green film), is then 450～550 DEG C of heating 1～5 minute at maximum sintering temperature, thereby change into polyimide by polyamic acid, can obtain in addition the polyimide film of the solvent of having removed with polyamic acid solvation.
But, be the polyimide film as thin as a wafer below 8.0 μ m if make thickness by method in the past as described above, due to its thin be therefore very easy in film end when the masking to occur from make pin eat into the cracking that starts of hole, fold when carrying and thereby the problem of complications film rupture has productivity low such problem significantly.The bonding processing of height of this external cementability that improves film and Copper Foil, suppress the thermal contraction of film and increase the low thermal shrinkage processing of dimensional stability, with volume to volume mode and Copper Foil is bonding or the postprocessing working procedures of coating adhesive in, if the planarity of film is poor,, because therefore the thin of its easily produce fold and operational difficulty, therefore produce and cause yield rate to reduce such problem.
As the industrial manufacture method of the polyimide film as thin as a wafer below 8.0 μ m, for example, in patent documentation (1), (2), there is following method: after temporarily applying with coating machine, peel off, then this base film is directed into tenter machine manufacture on support film.In the method in order to prevent the fracture starting from pin hole of base film end, by by the polyimide film of preparing in addition together with base film by needle-penetration, thereby keep the intensity of film end.But the method must be prepared end and control the polyimide film of use separately, therefore spends cost, production efficiency variation, it is many that the corner producing during by needle-penetration becomes.In addition,, owing to not stretching in the time that base film is made, the therefore molecular orientation of controlling diaphragm width equably, is easy to cause the reduction of tear propogation resistance, the deterioration of planarity.Particularly for the polyimide film of thing as thin as a wafer, if planarity is poor, in the time of masking, rear operation adds the reason that becomes variety of issue man-hour.Set out by above reason, require to keep well planarity few efficient polyimide film and the manufacture method thereof as thin as a wafer of problem such as simultaneously break.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-285516 communique
Patent documentation 2: TOHKEMY 2009-13245 communique
Summary of the invention
Invent problem to be solved
The present invention is studied the solution of above-mentioned the problems of the prior art, and result has realized the present invention.Therefore, the object of this invention is to provide the film rupture that is difficult for occurring in masking, the problem such as fold while carrying, film thickness is thin polyimide film and the manufacture method thereof below 8.0 μ m.
For solving the method for problem
Polyimide film of the present invention, the thickness of film is below 8.0 μ m, the tear propogation resistance of film is more than 1.7N/mm, and the minimum value of ultrasonic transmission speed is 2.0km/ second.In addition the sheet stretch value that represents the planarity quality of film is preferably below 8mm.
In addition, the manufacture method of polyimide film of the present invention is characterised in that, polyamic acid solution is extruded into continuously on support membranaceous and stretch, be dried, thermal treatment, or the gel-film that coating is formed from support peel off and stretch, be dried, the manufacturing process of heat treated polyimide film, it is more than 1.60 making after extruding on support 200 DEG C of total stretching ratios (stretching ratio of the stretching ratio × width of length direction) that carry out below the film of the inter process of film stretching more than 70 DEG C.The relative viscosity ratio with respect to 4.0% Potassium Bromide liquid of the polyamic acid solution that in addition, masking is used is more than 1.40 below 1.80, to be preferably to create conditions.
The effect of invention
According to the present invention, can obtain film thickness is below 8.0 μ m, resistance to tearing and planarity excellence, in film making process, manufacturing procedure thereafter by film rupture, the few polyimide film as thin as a wafer of problem of carrying fold etc. to bring.Particularly implement research by polymkeric substance composition, polymer viscosity and drawing process etc. when manufacturing thickness and be the polyimide film as thin as a wafer below 8.0 μ m, thereby can be in industrial resistance to tearing and the planarity excellence manufactured efficiently, the polyimide film as thin as a wafer of the operation excellence that the production problem brought by the film rupture in masking, the conveying fold etc. that adds man-hour is few.
By use make tear propogation resistance and ultrasonic transmission speed and sheet stretch value for more than set value, film thickness is the thin polyimide film below 8.0 μ m, film rupture can prevent masking time, in addition by preventing by the conveying fold in postprocessing working procedures, cutting the bad problem of bringing etc., the problem that also helps avoid postprocessing working procedures, contributes to high speed.The heat lamination that can also suppress in client's operation in addition, adds the conveying fold in man-hour and/or the generation of complications.
Brief description of the drawings
Fig. 1 is the schematic diagram of measuring the test film of the tear propogation Resistance Value of film.
Fig. 2 is the schematic diagram of explanation diaphragm stretch value.
Fig. 3 is the schematic diagram of the measuring method of explanation ultrasonic transmission speed.
Embodiment
Below, polyimide film of the present invention and manufacture method thereof are specifically described.
In polyimide film of the present invention, the minimum value of ultrasonic transmission speed need to be 2.0km/ second.Observe tearing phenomenon of film in the angle with macroscopical, be equivalent to cut off molecular chain.What a large amount of molecular chains of crosscut were such tears, and resistance is large, is difficult for occurring.Thus, about tearing in the direction of the direction not being orientated in crosscut, because the molecular chain of crosscut is few, be therefore difficult for occurring.About ultrasonic transmission speed, if the orientation of the polyimide of this direction is carried out, and molecular structure is upright and outspoken and Young's modulus uprises, and really accelerates.That is, ultrasonic transmission speed is less, is more easy to tearing of film occurs, and becomes the film that is easy to break.In polyimide film of the present invention, ultrasonic transmission speed is preferably 2.1～3.0km/ second, more preferably 2.2～2.9km/ second.
In the present invention, the ultrasonic transmission speed of so-called polyimide film, for using the SONIC SHEET TESTER (SST-2500 type) of wild village business (strain) system, by the mensuration head of multisensor mode, measure ultrasonic pulse and transmit the value of needed time (being 12cm in this situation) between the certain distance of sheet specimens.Each angle of measuring is sent into 11.25 ° until 180 ° of totals are measured 16 places, the minimum value of whole measured values is made as to the ultrasonic transmission speed of this film.This measured value is the index at the party's molecular orientation upwards, and more orientation is more carried out.In addition, the polymerization degree is larger, and molecular chain is longer, and the composition that forms polyimide is more easy to get two dimensional structure, more, for upright and outspoken structure, has the faster tendency of ultrasonic transmission speed.Ultrasonic transmission speed is an index that can judge the upright and outspoken degree of orientation degree and the polymerization degree and molecular structure thereof.
In the present invention, the tear propogation resistance of so-called polyimide film, for the Elmendorf method of Tearing according to recording in JIS K7128-2 (formulation on November 20th, 1998), use Japan's essence mechanism to make made light loading tear tester and measure the value obtaining.Resistance when this measured value represents film cracking, therefore the difficulty of tearing of thickness direction entirety has been considered in expression, more film is more not easy to crack can to say this measured value.In addition, about the tear propogation resistance in the present invention, length direction and width to film are measured, and a wherein low side's value are made as to the tear propogation resistance of film.Here the length direction of so-called film, the direction of membrane flow in the operation while referring to film manufacture.In addition, the width of so-called film, for the orthogonal direction of the length direction of film.
In polyimide film of the present invention, tear propogation resistance need to be more than 1.7N/mm, preferably, and more preferably more than 1.8N/mm, more preferably more than 1.9N/mm.If tear propogation resistance is little, due to little to the resistance of cracking, therefore film ftractures and is easy to occur the problems such as film rupture.
In polyimide film of the present invention, the thickness of film is below 8.0 μ m, more than being preferably 3.0 μ m, and more preferably 4.0～7.5 μ m.Film thickness is thinner, there is the lower fold of rigidity of film be more easy to sneak into and make to be easy to occur such problem by tortuous, the mobile bad film rupture bringing, but be more than 1.7N/mm by making tear propogation resistance, the minimum value of ultrasonic transmission speed is the 2.0km/ film of second, even thereby the thickness of film is below 8.0 μ m, also can masking.
The polyimide film of the present invention that meets above-mentioned characteristic preferably by polyamic acid solution is extruded into continuously on support membranaceous and stretch, be dried, thermal treatment, or the gel-film that coating is formed from support peel off and stretch, be dried, heat-treating methods manufactures.Polyimide film of the present invention is preferably by after extruding polyamic acid on support, more than 70 DEG C 200 DEG C of total stretching ratios (stretching ratio of the stretching ratio × width of length direction) that carry out below the film of the inter process of film stretching be 1.60 with on manufacture.Total stretching ratio of film is more preferably more than 1.70, further more preferably more than 1.80.The upper limit of total stretching ratio of film is generally 3.00 times of left and right.The gel-film with self-supporting of peeling off from support is preferably by stretching in the longitudinal direction by draw roll control translational speed.Preferably with the stretching ratio of length direction be preferably 1.05 times above below 2.00 times, more preferably 1.10 times above below 1.60 times, more preferably 1.10 times of above 1.50 times of following multiplying powers are implemented.In addition the stretching of length direction can be divided into 2 stages with on carry out.The gel-film being stretched in the longitudinal direction preferably, so that state that fixture is controlled both ends at width is directed in tenter machine, moves on one side together with tenter clip, stretches on one side on width.Preferably with the stretching ratio of width be preferably 1.05 times above below 2.00 times, more preferably 1.10 times above below 1.80 times, more preferably 1.10 times of above 1.70 times of following multiplying powers are implemented.By controlling so that more than 70 DEG C 200 DEG C of total stretching ratios (stretching ratio of the stretching ratio × width of length direction) that carry out below the film of the inter process of film stretching be more than 1.60, thereby can make the orientation of film width consistent equably, can obtain the good polyimide film of planarity.
Be orientated in order to control in the face of polyimide film, imidization reaction fully carry out and solvent evaporation less, the method for the more than 70 DEG C inter process 200 DEG C below enforcement stretching that the mobility of polymer molecular chain is higher is the most resultful.Temperature below 70 DEG C, imidization reaction is not carried out fully, and it is difficult being therefore orientated efficiently control by stretching.When stretching in the high operation of 200 DEG C of temperature of this external ratio, usual solvents can be evaporated, therefore the poor fluidity of polymer molecular chain, stretch and become difficulty, or due to therefore can be on the width uneven consistent difficulty that becomes equably that makes to be oriented on width of degree of drawing of uneven drying.
It is more than 1.40 to manufacture that polyimide film of the present invention preferably makes the relative viscosity ratio with respect to 4.0% Potassium Bromide liquid of the polyamic acid solution using in masking.Tearing of film is equivalent to peel the intermolecular combination of polyimide molecule, the winding of molecular chain.And molecular weight is larger, the winding of the intermolecular combination in film, molecular chain is larger.Therefore, be less than at 1.40 o'clock in the relative viscosity with respect to 4.0% Potassium Bromide liquid of polyamic acid solution, be difficult for obtaining polyimide molecule intermolecular forces each other, the winding of molecular chain, be therefore easy to occur the cracking of film, therefore not preferred.In addition, in the present invention, the relative viscosity with respect to 4.0% Potassium Bromide liquid of polyamic acid solution is more preferably more than 1.40 below 1.80, further more preferably more than 1.50 below 1.80, further more preferably more than 1.60 below 1.80.Exceed 1.80 in the relative viscosity of polyamic acid solution, the viscosity of polymkeric substance is too high, and therefore the pressure-losses of wayward mouthful of mould, is therefore difficult for discharging equably from mouth mould on width sometimes, is easy to form the uneven thickness of film.
Then, the gel-film after stretch processing is preferably dried in arid region.The in the situation that of heating by hot blast etc. in arid region, also preferably use arrange can by the hot blast using (wrap solvent-laden air, moisten into air) nozzle of exhaust, prevent from sneaking in arid region the hot blast that uses method.The hot blast temperature of arid region is preferably 150 DEG C of above 350 DEG C of following scopes.In addition, be preferably 5 seconds time of drying～about 10 minutes, more preferably 10 seconds～5 minutes.In addition not only can use hot blast, and can use radiation heating.
Polyimide film is by implementing suitable thermal treatment, thereby in polymer chain molecule, carry out and mechanical characteristics (to the weather resistance of external force) raising with the intermolecular imidization of polymer chain, therefore preferably carried out dry film in above-mentioned arid region and be further heat-treated.Thermal treatment is used the known methods such as hot blast, electric heater (such as infrared heater etc.) to carry out.Heat-treat condition is preferably adjusts well heater output and hot blast temperature etc. so that film L value is more than 30 below 55, final treatment condition be more than 250 DEG C below 500 DEG C and the treatment time be that the scope of 15 seconds～20 minutes is suitably carried out.In thermal treatment, if heating film sharp produces the undesirable conditions such as surface imperfection increase, therefore heating means are preferably suitably selected.Carry out heat treated film and be cooled, be wound in winding core.
The film thickness obtaining by aforesaid method is that 8.0 μ m are following, preferred film thicknesses is the polyimide film below the above 8.0 μ m of 3.0 μ m; the resistance to tearing of film and planarity excellence; therefore be easy in industrial production; add the operability excellence in man-hour, therefore expect to be widely used in the basement membrane of flexible printed board and the covering purposes taking the protection of electroconductive circuit, insulation as object etc.
As the polyamic acid of the precursor as polyimide in the present invention, formed by aromatic tetracarboxylic acid's class and aromatic diamines, be preferably by the repeating unit shown in following formula [I] and form.
[changing 1]
In above-mentioned formula, R1 is the 4 valency organic groups with at least 1 aromatic ring, and its carbonatoms is below 25, and R2 is the divalent organic group with at least 1 aromatic ring, and its carbonatoms is below 25.
In the present invention, aromatic tetracarboxylic acid's class of polyamic acid and the mol ratio of aromatic diamines as the precursor of polyimide are aggregated to equal substantially 1 ratio, but can be also more than 0.82 in mol ratio, be preferably in more than 0.90 scope, with respect to the opposing party, a side coordinates superfluously, taking mol ratio as more than 0.980, more preferably more than 0.985, more preferably more than 0.990 be aggregated.
So-called polyimide film in the present invention, refers to the with an organic solvent middle polyamic acid dissolving, and film imidization is made, and the polyamic acid in organic solvent solution can, partly by imidization, also can contain a small amount of mineral compound.
As the concrete example of above-mentioned aromatic tetracarboxylic acid's class, can enumerate Pyromellitic Acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic, 2,3 ', 3,4 '-bibenzene tetracarboxylic, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, 2,3,6,7-naphthalenetetracarbacidic acidic, 2, two (3, the 4-dicarboxyl phenyl) propane of 2-, pyridine-2,3,5,6-tetracarboxylic acid or their acid anhydrides or acid dianhydride or by these sour ester cpds or the derivative aromatic tetracarboxylic acid's class of halogenide.
As the concrete example of above-mentioned aromatic diamines, can enumerate Ursol D, mphenylenediamine, p-diaminodiphenyl, p dimethylamine, 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, 1,5-diaminonaphthalene, 3,3 '-dimethoxy benzidine, Isosorbide-5-Nitrae-bis-(3-methyl-5-aminophenyl) benzene and their derivative.
As the combination of aromatic tetracarboxylic acid's composition and aromatic diamine composition that is particularly suitable for polyimide in method of the present invention, can enumerate pyromellitic acid anhydride and 4,4 '-diamino-diphenyl ether and 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride and 4, the combination of 4 '-diamino-diphenyl ether, is preferably their copolymerization and/or the copolymerization of Ursol D in addition.In addition,, as long as not encumbering scope of the present invention, can also in the time of masking, carry out moulding with polylayer forest form.
In the present invention, as the concrete example of the organic solvent using in order to form polyamic acid solution, can enumerate N, dinethylformamide, N, the polar organic acid amides series solvents such as N-N,N-DIMETHYLACETAMIDE and METHYLPYRROLIDONE, these organic solvents can use separately or two or more is used in combination, but non-solvent that also can be such with benzene, toluene and dimethylbenzene is used in combination.In addition, in the present invention, the organic solvent using in order to form polyamic acid solution is hydrolyzed the solvent that forms amine by use, thereby can measure residual solvent.
The organic solvent solution of the polyamic acid using in the present invention contains and is preferably 5～40 % by weight, and the more preferably solids component of 10～30 % by weight, preferably can carry out stable liquor charging.
Polyreaction can be in organic solvent, stir on one side and/or mix, and carries out continuously 10 minutes～30 hours on one side, but also can as required polyreaction be separated, or make temperature upper and lower the temperature range of 0～80 DEG C.
In this case, the order of addition of two reactant is not particularly limited, but preferably in the solution of aromatic diamines, adds aromatic tetracarboxylic acid's class.
So-called in polyreaction, carrying out vacuum defoamation, is the effective ways of the organic solvent solution of the polyamic acid good for the manufacture of quality.In addition, can before polyreaction, in aromatic diamines, add a small amount of end closure agent and control polymerization.
As the concrete example of the closed loop catalyzer using in the present invention, can enumerate the hetero ring type tertiary amines such as the aliphatic tertiary amine such as Trimethylamine 99, triethylamine and isoquinoline 99.9, pyridine, picoline etc., preferably use at least one amine of selecting from hetero ring type tertiary amine.
As the concrete example of the dewatering agent using in the present invention, can enumerate the aromatic carboxylic acid such as aliphatic carboxylic acid acid anhydride and the benzoyl oxide acid anhydrides such as diacetyl oxide, propionic anhydride, butyryl oxide etc., but be preferably diacetyl oxide and/or benzoyl oxide.
Closed loop catalyzer is preferably with respect to the content of polyamic acid that to make the content (mole) content of/polyamic acid (mole) of closed loop catalyzer be 0.5～8 scope.
In addition, dewatering agent is preferably with respect to the content of polyamic acid that to make the content (mole) content of/polyamic acid (mole) of dewatering agent be 0.1～4 scope.In addition, in this case, can be used together methyl ethyl diketone isogel delayed-action activator.
As the exemplary process of being manufactured polyimide film by the organic solvent solution of polyamic acid, can enumerate the organic solvent solution of the polyimide acid that does not contain closed loop catalyzer and dewatering agent is cast to support and is shaped to film from the mouth mould with slit, make the gel-film with self-supporting by carry out heat drying on support, then from support stripping film, further carry out the hot closed loop method of imidization by high temperature carrying out dry heat processing; With the organic solvent solution of the polyamic acid that contains closed loop catalyzer and dewatering agent is cast to support and is shaped to membranaceous from the mouth mould with slit, on support, make a part carry out imidization and make the film with self-supporting, then from support stripping film, carry out heat drying/imidization, the chemical closed loop method of heat-treating.The present invention can adopt above-mentioned arbitrary closed-loop policy, although the equipment that chemistry closed loop method need to make the organic solvent solution of polyamic acid contain closed loop catalyzer and dewatering agent, but from obtain the gel-film aspect with self-preservation with the short period of time, can be described as preferred method.In addition, so-called gel-film in the present invention, refer to comprise polyimide precursor and/or partly imidization the polyimide film of solvent.
[embodiment]
Below, by embodiment, the present invention is described, but the present invention is not limited to these embodiment.Evaluation method and the metewand of each characteristic of describing in above-mentioned description and following embodiment in addition, are as follows.
(1) tear propogation resistance
Tear propogation resistance is the Elmendorf method of Tearing of recording according in JIS K7128-2 (formulation on November 20th, 1998), use Toyo Co., Ltd.'s essence mechanism do the light loading tear tester of No.193 form D, the method for recording in the process specifications with the 2nd edition distribution May in 2008 is measured the value obtaining.About sample size, as shown in Figure 1, the film of specimen size 63.5mm length × 50mm width, cut-in length 12.7mm is taked respectively at Cong Mo center on length direction and width.Determination block number is 1, measures to measure 25 DEG C × 60%RH of atmosphere, length direction and the little side of width intermediate value is made as to the tear propogation Resistance Value of this film.
(2) film thickness
By overlapping film 10, measure film thickness with the digital micrometer M-30 processed of SONY society, by this one-tenth-value thickness 1/10 divided by 10 the 1st of the radix point of value round up and value be made as film thickness.
(3) diaphragm stretch value
About the sheet stretch value of film, using the central authorities of film as center, cut apart closely so that each film width is 500mm, sample length direction 6.5m spreading out equably on smooth plate respectively, bracing wire between the both ends on the limit of 6.5m, measure the distance between limit and the line of film at end and central part, its absolute value is made as to the sheet stretch value (Fig. 2) of film.In each sheet stretch value of having cut apart, the value of maximum is made as to the sheet stretch value of this film.
(4) ultrasonic transmission speed
Use the SONIC SHEET TESTER (SST-2500 type) of wild village business (strain) system to measure.Using the central authorities of film as center, cut apart closely each film with 262mm interval, respectively at the long film of the 8 sample length direction 250mm of place.Measure ultrasonic pulse at the center from each sample film to propagating the needed time (Fig. 3) diameter 12cm.By the mensuration head of multisensor mode, within 4 seconds, to measure the orientation at 1 place.Each angle of measuring is sent into 11.25 ° until 180 °, measure and add up to 16 places, the ultrasonic transmission speed that the minimum value of whole measured values is made as to this film is (in the thin film below 8.0 μ m, owing to measuring under the condition that impact is strong, speed is low of sometimes bringing in the orientation by molecular chain and density structure, therefore for make speed saturated and with 30 overlapping mensuration).
(5) relative viscosity
The polyamic acid solution that masking is used is diluted to the test sample of 0.5% solution and 4.0% lithiumbromide/N,N-dimethylacetamide solution according to JIS K2283 (on November 20th, 2000 revised edition.The viscometer model 350 of キ ャ ノ Application-マ ニ Application グ ミ Network ロ viscometer, temperature: 30 DEG C), measure lowering time, its lowering time is made as to relative viscosity than the value calculating with following formula.
Relative viscosity (η r)=2 × Ln (Ts/Tb)
Ts: the lowering time (s) of polyamic acid solution for viscosimetric analysis
The lowering time (s) of Tb:4.0% lithiumbromide/N,N-dimethylacetamide solution.
The inflation method of polyamic acid solution for viscosimetric analysis
1. polymer concentration is measured
In the aluminium vessel of known weight in advance, add polyamic acid solution to carry out gravimetry.Then, in the baking oven of heating direct to 100 DEG C, heat after 0.5 hour, be warming up to 350 DEG C with 10 DEG C/min speed, 350 DEG C of heating 2 hours.After heating finishes, be fetched into outside, after cooling 15 minutes, gravimetry, calculates polymer concentration according to following formula.
Polymer concentration (%)=100-{ (B-C)/(B-A) × 100 }
A: aluminium vessel weight (g)
B: the polymers soln weight (g) before aluminium vessel weight (g)+heating
C: the polymer weight (g) after aluminium vessel weight (g)+heating
2. the adjustment of polyamic acid solution for viscosimetric analysis
In the aluminium vessel of known weight in advance, add polyamic acid solution to carry out gravimetry.Add 4.0% lithiumbromide/N,N-dimethylacetamide solution of the amount of following formula so that polymer concentration is 0.5%.
4.0% lithiumbromide/N,N-dimethylacetamide solution addition (g)={ (E-D) × F/100 }/0.005-(E-D)
D: aluminium vessel weight (g)
E: aluminium vessel weight (g)+polymers soln weight (g)
F: polymer concentration (%).
(6) Young's modulus
Young's modulus is according to JIS-K7127 (revised edition on August 20th, 1999), at room temperature by the Tensilon type extensometer of ORIENREC society system, in the tension force-deformation curve obtaining with draw speed 300mm/ minute, obtain (gradient × initial specimen length of initial riser portions)/(specimen width × sample thickness) by the gradient of initial riser portions.About sample, Cong Mo takes at center the sample of size 10mm × 250mm, at chuck spacing 100mm, under the atmosphere of 25 DEG C of 60%RH, measures.Length direction and width at film are measured, and a side little value are made as to the Young's modulus of this film.
(7) masking (easiness of masking)
The situation of the problems such as the film rupture that does not have generation to be caused by fold, cracking in the masking of film length 5000m is made as to zero, the situation that the problems referred to above have occurred is made as ×.
(8) processibility (easiness of processing)
Utilize roll coater, on polyimide film, being coated with epoxy is that caking agent is so that dried overall coating thickness is 12.5 μ m, after 80 DEG C × 2 minutes and 120 DEG C × 5 minutes heat dryings, add thermo-compressed with temperature 50 C, line pressure 5Kg/cm, speed 2m/min, tension force 1kg/m by roll laminating machine and release paper and obtain mulch film.According to following benchmark evaluation machining status.
Zero: without bending, fold
Δ: bending, fold partly exist,
×: whole there is bending, fold.
［ embodiment 1 ］
Prepare pyromellitic acid anhydride (molecular weight 218.12)/3 taking molar ratio computing as 65/35/82/18 ratio, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (molecular weight 294.22)/4,4 '-diamino-diphenyl ether (molecular weight 200.24)/Ursol D (molecular weight 108.14) (this monomer composition ratio is made as to A), at N, in N-N,N-DIMETHYLACETAMIDE, make 20 % by weight solution and carry out polymerization, obtaining is the polyamic acid solution of 3800 pools at 25 DEG C.The relative viscosity with respect to 4.0% Potassium Bromide liquid of this solution is 1.59.
In this polyamic acid solution, with respect to being dried of polyamic acid unit mixing 2.0mol N,N-dimethylacetamide, with respect to the diacetyl oxide of polyamic acid unit mixing 4.0mol, with respect to β-picoline of polyamic acid unit mixing 4.0mol, adjust polyamic acid solution.
This polyamic acid solution is extruded from the T-shaped mould of mouth mould slit width 1.3mm, length 2000mm, the ratio of support speed/mouth mould velocity of discharge is made as to 10.6, be cast on the metal support of 80 DEG C of rotation and obtain the gel-film with self-supporting.This gel-film is peeled continuously from support, in film length direction, be stretched to 1.22 times of one side rollers on indoor one side of 70 DEG C and carry.On one side pierce through continuously on one side and gel-film is fixed on to the needle plate on chain with the two ends that roller is pinned gel-film, the air 5～10 seconds of 250 DEG C of jetting on needle plate, thereby first dry immobilized gel film end.To on needle plate, on width, be stretched to 1.62 times with the gel-film that pin has been fixed two ends, then within 20～40 seconds, be dried by the air of 250 DEG C of jetting in tenter machine, then use electric heater to implement thermal treatment until 450 DEG C, then relax while be cooled to room temperature.Then film end is taken off from pin, by the edge of end of cutting film, thereby obtain the polyimide film of width 2300mm, thickness 7.8 μ m.There are not fold, complications etc. in film in masking, can carry out length 5000m masking stably above.The tear propogation resistance of the film of gained is 1.9N/mm, and ultrasonic transmission speed is 2.28km/ second.In addition, sheet stretch value is 2mm, and processibility is also good.
［ embodiment 2 ］
Prepare pyromellitic acid anhydride (molecular weight 218.12)/3 taking molar ratio computing as 75/25/71/29 ratio, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (molecular weight 294.22)/4,4 '-diamino-diphenyl ether (molecular weight 200.24)/Ursol D (molecular weight 108.14) (this monomer composition ratio is made as to B), at N, in N-N,N-DIMETHYLACETAMIDE, make 20 % by weight solution and carry out polymerization, obtaining is the polyamic acid solution of 3800 pools at 25 DEG C.The relative viscosity with respect to 4.0% Potassium Bromide liquid of this solution is 1.58.The stretching ratio that makes film length direction is 1.24, and the stretching ratio of width is 1.51, in addition, and masking similarly to Example 1, the polyimide film of acquisition width 2300mm, thickness 7.5 μ m.There are not fold, complications etc. in film in masking, can carry out length 5000m masking stably above.The tear propogation resistance of the film of gained is 2.0N/mm, and ultrasonic transmission speed is 2.33km/ second.In addition, sheet stretch value is 3mm, and processibility is also good.
［ embodiment 3 ］
Prepare pyromellitic acid anhydride (molecular weight 218.12)/3 taking molar ratio computing as 75/25/75/25 ratio, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (molecular weight 294.22)/4,4 '-diamino-diphenyl ether (molecular weight 200.24)/Ursol D (molecular weight 108.14) (this monomer composition ratio is made as to C), at N, in N-N,N-DIMETHYLACETAMIDE, make 19 % by weight solution and carry out polymerization, obtaining is the polyamic acid solution of 3800 pools at 25 DEG C.The relative viscosity with respect to 4.0% Potassium Bromide liquid of this solution is 1.65.
In this polyamic acid solution, with respect to being dried of polyamic acid unit mixing 2.0mol N,N-dimethylacetamide, with respect to the diacetyl oxide of polyamic acid unit mixing 4.0mol, with respect to β-picoline of polyamic acid unit mixing 4.0mol, adjust polyamic acid solution.
This polyamic acid solution is extruded from the T-shaped mould of mouth mould slit width 1.3mm, length 2000mm, the ratio of support speed/mouth mould velocity of discharge is made as to 9.8, be cast on the metal support of 80 DEG C of rotation and obtain the gel-film with self-supporting.This gel-film is peeled continuously from support, in film length direction, be stretched to 1.28 times of one side rollers on indoor one side of 70 DEG C and carry.On one side pierce through continuously on one side and gel-film is fixed on to the needle plate on chain with the two ends that roller is pinned gel-film, by jet the air 5～10 seconds of 250 DEG C on needle plate, thus first dry immobilized gel film end.To on needle plate, on width, be stretched to 1.46 times with the gel-film that pin has been fixed two ends, then within 20～40 seconds, be dried by the air of 250 DEG C of jetting in tenter machine, then use electric heater to implement thermal treatment until 450 DEG C, then relax while be cooled to room temperature.Then film end is taken off from pin, by the edge of end of cutting film, thereby obtain the polyimide film of width 2100mm, thickness 7.8 μ m.There are not fold, complications etc. in film in masking, can carry out length 5000m masking stably above.The tear propogation resistance of the film of gained is 2.2N/mm, and ultrasonic transmission speed is 2.27km/ second.In addition, sheet stretch value is 6mm, and processibility is also good.
［ embodiment 4 ］
Prepare pyromellitic acid anhydride (molecular weight 218.12)/3 taking molar ratio computing as 65/35/82/18 ratio, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (molecular weight 294.22)/4,4 '-diamino-diphenyl ether (molecular weight 200.24)/Ursol D (molecular weight 108.14) (this monomer composition ratio is made as to A), at N, in N-N,N-DIMETHYLACETAMIDE, make 20 % by weight solution and carry out polymerization, obtaining is the polyamic acid solution of 3800 pools at 25 DEG C.The relative viscosity with respect to 4.0% Potassium Bromide liquid of this solution is 1.64.
In this polyamic acid solution, with respect to being dried of polyamic acid unit mixing 2.0mol N,N-dimethylacetamide, with respect to the diacetyl oxide of polyamic acid unit mixing 4.0mol, with respect to β-picoline of polyamic acid unit mixing 4.0mol, adjust polyamic acid solution.
This polyamic acid solution is extruded from the T-shaped mould of mouth mould slit width 1.3mm, length 2000mm, the ratio of support speed/mouth mould velocity of discharge is made as to 12.7, be cast on the metal support of 80 DEG C of rotation and obtain the gel-film with self-supporting.This gel-film is peeled continuously from support, in film length direction, be stretched to 1.22 times of one side rollers on indoor one side of 70 DEG C and carry.On one side pierce through continuously on one side and gel-film is fixed on to the needle plate on chain with the two ends that roller is pinned gel-film, by jet the air 5～10 seconds of 250 DEG C on needle plate, thus first dry immobilized gel film end.To on needle plate, on width, be stretched to 1.55 times with the gel-film that pin has been fixed two ends, then within 20～40 seconds, be dried by the air of 250 DEG C of jetting in tenter machine, then use electric heater to implement thermal treatment until 450 DEG C, then relax while be cooled to room temperature.Then film end is taken off from pin, by the edge of end of cutting film, thereby obtain the polyimide film of width 2100mm, thickness 6.8 μ m.There are not fold, complications etc. in film in masking, can carry out length 5000m masking stably above.The tear propogation resistance of the film of gained is 1.9N/mm, and ultrasonic transmission speed is 2.24km/ second.In addition, sheet stretch value is 4mm, and processibility is also good.
［ embodiment 5 ］
The ratio of support speed/mouth mould velocity of discharge is made as to 15.9, in addition, masking similarly to Example 4, thereby the polyimide film of acquisition width 2100mm, thickness 5.1 μ m.There are not fold, complications etc. in film in masking, can carry out length 5000m masking stably above.The tear propogation resistance of the film of gained is 1.9N/mm, and ultrasonic transmission speed is 2.24km/ second.Adopt commercially available winding machine to carry out cut roll, also obtain the film volume of width 500mm, length 3000m.In addition, sheet stretch value is 6mm, and processibility is also good.
［ embodiment 6 ］
Prepare pyromellitic acid anhydride (molecular weight 218.12)/3 taking molar ratio computing as 75/25/71/29 ratio, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (molecular weight 294.22)/4,4 '-diamino-diphenyl ether (molecular weight 200.24)/Ursol D (molecular weight 108.14) (this monomer composition ratio is made as to B), in METHYLPYRROLIDONE, make 20 % by weight solution and carry out polymerization, obtaining is the polyamic acid solution of 3800 pools at 25 DEG C.The relative viscosity with respect to 4.0% Potassium Bromide liquid of this solution is 1.60.
In this polyamic acid solution, with respect to being dried of polyamic acid unit mixing 2.0mol METHYLPYRROLIDONE, with respect to the propionic anhydride of polyamic acid unit mixing 4.0mol, with respect to the pyridine of polyamic acid unit mixing 4.0mol, adjust polyamic acid solution.
This polyamic acid solution is extruded from the T-shaped mould of mouth mould slit width 1.3mm, length 2000mm, the ratio of support speed/mouth mould velocity of discharge is made as to 15.5, be cast on the metal support of 80 DEG C of rotation and obtain the gel-film with self-supporting.This gel-film is peeled continuously from support, in film length direction, be stretched to 1.22 times of one side rollers on indoor one side of 70 DEG C and carry.On one side pierce through continuously on one side and gel-film is fixed on to the needle plate on chain with the two ends that roller is pinned gel-film, by jet the air 5～10 seconds of 250 DEG C on needle plate, thus first dry immobilized gel film end.To on needle plate, on width, be stretched to 1.54 times with the gel-film that pin has been fixed two ends, then within 20～40 seconds, be dried by the air of 250 DEG C of jetting in tenter machine, then use electric heater to implement thermal treatment until 450 DEG C, then relax while be cooled to room temperature.Then film end is taken off from pin, by the edge of end of cutting film, thereby obtain the polyimide film of width 2100mm, thickness 6.0 μ m.There are not fold, complications etc. in film in masking, can carry out length 5000m masking stably above.The tear propogation resistance of the film of gained is 2.0N/mm, and ultrasonic transmission speed is 2.34km/ second.In addition, sheet stretch value is 2mm, and processibility is also good.
［ comparative example 1 ］
Prepare pyromellitic acid anhydride (molecular weight 218.12)/3 taking molar ratio computing as 65/35/82/18 ratio, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (molecular weight 294.22)/4,4 '-diamino-diphenyl ether (molecular weight 200.24)/Ursol D (molecular weight 108.14) (this monomer composition ratio is made as to A), at N, in N-N,N-DIMETHYLACETAMIDE, make 20 % by weight solution and carry out polymerization, obtaining is the polyamic acid solution of 3200 pools at 25 DEG C.The relative viscosity with respect to 4.0% Potassium Bromide liquid of this solution is 1.32.
In this polyamic acid solution, with respect to being dried of polyamic acid unit mixing 2.0mol N,N-dimethylacetamide, with respect to the diacetyl oxide of polyamic acid unit mixing 4.0mol, with respect to β-picoline of polyamic acid unit mixing 4.0mol, adjust polyamic acid solution.
This polyamic acid solution is extruded from the T-shaped mould of mouth mould slit width 1.3mm, length 2000mm, the ratio of support speed/mouth mould velocity of discharge is made as to 10.6, be cast on the metal support of 80 DEG C of rotation and obtain the gel-film with self-supporting.This gel-film is peeled continuously from support, in film length direction, be stretched to 1.22 times of one side rollers on indoor one side of 70 DEG C and carry.On one side pierce through continuously on one side and gel-film is fixed on to the needle plate on chain with the two ends that roller is pinned gel-film, by jet the air 5～10 seconds of 250 DEG C on needle plate, thus first dry immobilized gel film end.To on needle plate, on width, be stretched to 1.61 times with the gel-film that pin has been fixed two ends, then within 20～40 seconds, be dried by the air of 250 DEG C of jetting in tenter machine, then use electric heater to implement thermal treatment until 450 DEG C, then relax while be cooled to room temperature.Then film end is taken off from pin, by the edge of end of cutting film, thereby obtain the polyimide film of width 2300mm, thickness 7.8 μ m.But, reach after above-mentioned condition, after 500m masking, there is cracking from film end and generation film rupture.Reattempt under the same conditions, but in the masking of hundreds of rice left and right, film rupture occurs again, stably continuous masking.The tear propogation resistance of the film before film is about to break is 1.5N/mm, and ultrasonic transmission speed is 2.22km/ second.In addition, sheet stretch value is 6mm, and processibility is good.
［ comparative example 2 ］
Prepare pyromellitic acid anhydride (molecular weight 218.12)/4 taking molar ratio computing as 100/100 ratio, 4 '-diamino-diphenyl ether (molecular weight 200.24) (this monomer composition ratio is made as to D), at N, in N-N,N-DIMETHYLACETAMIDE, make 23 % by weight solution and carry out polymerization, obtaining is the polyamic acid solution of 3200 pools at 25 DEG C.The relative viscosity with respect to 4.0% Potassium Bromide liquid of this solution is 1.38.
In this polyamic acid solution, with respect to being dried of polyamic acid unit mixing 2.0mol N,N-dimethylacetamide, with respect to the diacetyl oxide of polyamic acid unit mixing 4.0mol, with respect to β-picoline of polyamic acid unit mixing 4.0mol, adjust polyamic acid solution.
This polyamic acid solution is extruded from the T-shaped mould of mouth mould slit width 1.3mm, length 2000mm, the ratio of support speed/mouth mould velocity of discharge is made as to 12.0, be cast on the metal support of 80 DEG C of rotation and obtain the gel-film with self-supporting.This gel-film is peeled continuously from support, in film length direction, be stretched to 1.22 times of one side rollers on indoor one side of 70 DEG C and carry.On one side pierce through continuously on one side and gel-film is fixed on to the needle plate on chain with the two ends that roller is pinned gel-film, by jet the air 5～10 seconds of 250 DEG C on needle plate, thus first dry immobilized gel film end.To on needle plate, on width, be stretched to 1.55 times with the gel-film that pin has been fixed two ends, then within 20～40 seconds, be dried by the air of 250 DEG C of jetting in tenter machine, then use electric heater to implement thermal treatment until 450 DEG C, then relax while be cooled to room temperature.Then film end is taken off from pin, by the edge of end of cutting film, thereby obtain the polyimide film of width 2200mm, thickness 7.6 μ m.But, reach after above-mentioned condition, after 2000m masking on gel-film conveying roller film generation fold, there is in addition film rupture from film end cracking.The tear propogation resistance of the film before film is about to break is 1.4N/mm, and ultrasonic transmission speed is 1.62km/ second.In addition, sheet stretch value is 9mm, has to the membrane portions after covering processing noticeable fold.
［ comparative example 3 ］
Prepare pyromellitic acid anhydride (molecular weight 218.12)/3 taking molar ratio computing as 94/6/87/13 ratio, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (molecular weight 294.22)/4,4 '-diamino-diphenyl ether (molecular weight 200.24)/Ursol D (molecular weight 108.14) (this monomer composition ratio is made as to E), at N, in N-N,N-DIMETHYLACETAMIDE, make 19 % by weight solution and carry out polymerization, obtaining is the polyamic acid solution of 3800 pools at 25 DEG C.The relative viscosity with respect to 4.0% Potassium Bromide liquid of this solution is 1.60.
In this polyamic acid solution, with respect to being dried of polyamic acid unit mixing 2.0mol N,N-dimethylacetamide, with respect to the diacetyl oxide of polyamic acid unit mixing 4.0mol, with respect to β-picoline of polyamic acid unit mixing 4.0mol, adjust polyamic acid solution.
This polyamic acid solution is extruded from the T-shaped mould of mouth mould slit width 1.3mm, length 2000mm, the ratio of support speed/mouth mould velocity of discharge is made as to 13.5, be cast on the metal support of 80 DEG C of rotation and obtain the gel-film with self-supporting.This gel-film is peeled continuously from support, in film length direction, be stretched to 1.15 times of one side rollers on indoor one side of 70 DEG C and carry.On one side pierce through continuously on one side and gel-film is fixed on to the needle plate on chain with the two ends that roller is pinned gel-film, by jet the air 5～10 seconds of 250 DEG C on needle plate, thus first dry immobilized gel film end.To on needle plate, on width, be stretched to 1.35 times with the gel-film that pin has been fixed two ends, then within 20～40 seconds, be dried by the air of 250 DEG C of jetting in tenter machine, then use electric heater to implement thermal treatment until 450 DEG C, then relax while be cooled to room temperature.Then film end is taken off from pin, by the edge of end of cutting film, thereby obtain the polyimide film of width 2100mm, thickness 5.5 μ m.But, reach after above-mentioned condition, after 1700m masking on gel-film conveying roller film generation fold, occur significantly tortuous, film cracking and film rupture occurs when in addition film end being taken off from pin.The tear propogation resistance of the film before film is about to break is 1.6N/mm, and ultrasonic transmission speed is 1.94km/ second.In addition, sheet stretch value is 12mm, and for the film covering after processing, almost whole face all exists fold.
Above result is concluded and is shown in Table 1.
[table 1]
Industry utilizability
Below thin thickness to the 8.0 μ m of the polyimide film being obtained by the present invention; but resistance to tearing and planarity excellence; therefore be easy in industrial production; in addition add the operability excellence in man-hour, expect to be widely used in the basement membrane of flexible printed board and the covering purposes taking the protection of electroconductive circuit, insulation as object etc.
Claims (6)
1. a polyimide film, the tear propogation Resistance Value of film is more than 1.7N/mm, and the minimum value of the ultrasonic transmission speed of film is that more than 2.0km/ second film thickness is below 8.0 μ m.
2. polyimide film according to claim 1, diaphragm stretch value is below 8mm.
3. polyimide film according to claim 1 and 2, the form of polyimide film is that following, the more than length 1000m polyimide film of the above 3000mm of width 500mm is rolled up.
4. the manufacture method of a polyimide film, polyamic acid solution be extruded into continuously on support membranaceous and stretching, dry, thermal treatment, or the gel-film that coating is formed is peeled off and stretches from support, dry, in the manufacturing process of heat treated polyimide film, it is more than 1.60 making after extruding on support 200 DEG C of total stretching ratios (stretching ratio of the stretching ratio × width of length direction) that carry out below the film of the inter process of film stretching more than 70 DEG C, the tear propogation Resistance Value of manufacturing film is more than 1.7N/mm, and the minimum value of the ultrasonic transmission speed of film is more than 2.0km/ second, film thickness is the polyimide film below 8.0 μ m.
5. the manufacture method of polyimide film according to claim 4, polyamic acid solution is extruded into continuously on support membranaceous and stretch, be dried, thermal treatment, or the gel-film that coating is formed from support peel off and stretch, be dried, the manufacturing process of heat treated polyimide film, the relative viscosity with respect to 4.0% Potassium Bromide liquid of the polyamic acid solution using is more than 1.40 below 1.80.
6. according to the manufacture method of the polyimide film described in claim 4 or 5, diaphragm stretch value is below 8mm.
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| CN106008969A (en) * | 2015-03-27 | 2016-10-12 | 杜邦-东丽株式会社 | Polyimide film |
| CN109486189A (en) * | 2018-11-09 | 2019-03-19 | 李梅 | A kind of TPI film and preparation method thereof for FPC industry |
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| JP6765272B2 (en) * | 2016-09-30 | 2020-10-07 | 東レ・デュポン株式会社 | Polyimide film |
| JP7248394B2 (en) | 2017-09-29 | 2023-03-29 | 日鉄ケミカル＆マテリアル株式会社 | Polyimide film and metal-clad laminate |
| JP7405644B2 (en) | 2019-03-27 | 2023-12-26 | 日鉄ケミカル＆マテリアル株式会社 | Metal-clad laminates and circuit boards |
| KR20230154925A (en) * | 2021-06-07 | 2023-11-09 | 듀폰 도레이 컴파니, 리미티드 | Polyimide film for stretchable circuits, stretchable circuits, wearable devices |
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| JP2008285516A (en) * | 2007-05-15 | 2008-11-27 | Toyobo Co Ltd | Method for producing polyimide film |
| JP2009013245A (en) * | 2007-07-03 | 2009-01-22 | Toyobo Co Ltd | Polyimide film |
| JP2012143877A (en) * | 2011-01-06 | 2012-08-02 | Du Pont-Toray Co Ltd | Method for manufacturing polyimide film |
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| US4906731A (en) * | 1987-06-01 | 1990-03-06 | E. I. Du Pont De Nemours And Company | Polyimide molecular weight enhancement by solvent extraction |
| JP4448836B2 (en) * | 2000-04-20 | 2010-04-14 | 帝人株式会社 | Production method of polyimide film |
| US7871554B2 (en) * | 2005-04-14 | 2011-01-18 | Mitsubishi Gas Chemical Company, Inc. | Process for producing polyimide film |
| JP2007314596A (en) * | 2006-05-23 | 2007-12-06 | Toyobo Co Ltd | Polyimide roll film, copper-clad laminate, circuit board and method for producing polyimide roll film |
| JP5297740B2 (en) * | 2007-09-28 | 2013-09-25 | 新日鉄住金化学株式会社 | Laminate for heat conductive flexible substrate |
| JP2011116958A (en) * | 2009-10-28 | 2011-06-16 | Du Pont-Toray Co Ltd | Polyimide film and method for producing the same |
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| JP2008285516A (en) * | 2007-05-15 | 2008-11-27 | Toyobo Co Ltd | Method for producing polyimide film |
| JP2009013245A (en) * | 2007-07-03 | 2009-01-22 | Toyobo Co Ltd | Polyimide film |
| JP2012143877A (en) * | 2011-01-06 | 2012-08-02 | Du Pont-Toray Co Ltd | Method for manufacturing polyimide film |
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| CN106008969A (en) * | 2015-03-27 | 2016-10-12 | 杜邦-东丽株式会社 | Polyimide film |
| CN109486189A (en) * | 2018-11-09 | 2019-03-19 | 李梅 | A kind of TPI film and preparation method thereof for FPC industry |
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